TWI638842B - Colorless polyamide-imide resin and film thereof - Google Patents

Abstract

The present invention relates to a colorless polyamidoximine resin and a film thereof, and more particularly to a colorless transparent, excellent thermal stability and mechanical properties, and improved birefringence properties, which can be applied to a semiconductor insulating film, A polyamidoquinone imide resin and a film thereof in various fields such as a TFL-LCD insulating film, a passivation film, a liquid crystal backing film, a material for optical communication, a protective film for a solar cell, and a flexible display substrate.

Description

Colorless polyamidoximine resin and film thereof

The present invention relates to a colorless polyamidoximine resin and a film thereof, and more particularly to a colorless polyamidoxime which is excellent in thermal stability, mechanical properties and birefringence characteristics and can be applied to a substrate for a flexible display. Imine resin and its film.

The polyimide film is generally obtained by thinning a polyimide resin, and the polyimide resin is a solution polymerization method of an aromatic dianhydride with an aromatic diamine or an aromatic diisocyanate. After the polyglycine derivative is obtained, it is subjected to ring closure dehydration at a high temperature to carry out hydrazine imidization, thereby producing a highly heat resistant resin.

In order to prepare such a polyimide resin, pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) may be used as the aromatic dianhydride component, and diaminodiphenyl ether (ODA) may be used. ), p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), diaminodiphenylmethane (MDA), bisaminophenyl hexafluoropropane (HFDA) or the like as an aromatic diamine component.

The above-mentioned polyimine resin is excellent in oxidation resistance, heat resistance, radiation resistance, low-temperature property, chemical resistance, etc., and is widely used in automotive materials. Heat-resistant cutting-edge materials such as aerospace materials and spacecraft materials, as well as electronic coating materials such as insulating coating agents, insulating films, semiconductors, and electrode protective films for liquid crystal displays (TFT-LCDs).

However, polyimine resin exhibits a brown or yellow color due to its high aromatic ring density, low transmittance in the visible light region, and high birefringence. This is not suitable for use as an optical component.

In order to impart transparency to the dark brown and yellow polyimine, a linkage group (-O-, -SO ₂ -, -CO-, -CF ₃ CCF ₃ -, etc.) or The side chain with a relatively large free volume is introduced into the main chain to minimize the in-molecular and intramolecular charge transfer complexes and to have transparency.

However, the transparent polyimide film obtained in the above case lowers the heat resistance due to the introduced functional group. This phenomenon is caused by the charge transfer complex, and therefore, although the color becomes transparent, there is a problem that heat resistance is lowered. The reduction in heat resistance causes the transparent polyimide film to be limited in the field of advanced materials such as displays or semiconductors which require high operating temperatures. In order to solve the above problems, there has been a method in which a monomer and a solvent are purified and polymerized, but in this case, the improvement in the transmittance is not large.

Therefore, U.S. Patent No. 5,053,480 discloses a method of replacing an aromatic dianhydride with an aliphatic cyclic dianhydride component. In the case of a solution phase or a thin film, the transparency and color are obtained in comparison with the purification method. Improvement, but the improvement in penetration is still limited and cannot meet high penetration rates. In addition, there are also reduced results in terms of thermal and mechanical properties.

In addition, U.S. Patent Nos. 4,595,548, 4,603,061, 4,645,824, 4,895,972, 5,218,083, 5,093,453, 5,218,077, 5,367,046, 5,338,826, 5,986,036, 6,232,428, and Korean Patent Publication of Japanese Patent Publication No. 2003-0009437 discloses the use of a curved structure having a linking group of -O-, -SO ₂ -, CH ₂ - or the like to a (m)-position of a non-pair (p) position. A novel structure of an aromatic dianhydride having a substituent such as -CF ₃ and an aromatic diamine monomer, which improves the transmittance and color transparency within a limit that the thermal properties are not greatly lowered. Imine, but it still shows insufficientness in terms of birefringence properties.

On the other hand, the conventional glass substrate is difficult to achieve flexibility and is easily broken, so that there are many difficulties in practical use. A thin and light method, in addition to using a thin glass substrate, a method of removing the glass after coating the polyimide substrate on the existing glass substrate, and preparing on the polyimide film. Method etc. Colorless and transparent When the imide film is used in the field of display materials, it can be applied to display devices of various forms, and in addition to the advantages of being able to realize the flexible characteristics of the curved surface, it is also possible to realize a thin, light and not easily broken property.

Therefore, in order to apply the leuco-polyimine to the display, the display achieves excellent heat stability during the manufacturing process and has mechanical properties against tearing, while ensuring a viewing angle, a polyamidofluorene having a low birefringence value Imine resins have an urgent need.

A main object of the present invention is to provide a colorless polyamidoximine resin and a film thereof which are excellent in thermal stability, mechanical properties, and birefringence characteristics and can be used in a substrate for a flexible display.

Further, another object of the present invention is to provide a substrate for a flexible display which is improved in thermal stability, mechanical properties and birefringence characteristics.

In order to achieve the above object, a specific embodiment of the present invention provides a polyamidoximine resin which is obtained by copolymerization of an aromatic dianhydride and an aromatic dicarbonyl compound with an aromatic diamine. The imide of the obtained polyaminic acid, wherein the aromatic dicarbonyl compound is contained in an amount of from 1 to 50 mol% based on the total moles of the aromatic dianhydride and the aromatic dicarbonyl compound, and the aromatic The dianhydride comprises a component selected from the group consisting of (i) 4,4'-hexafluoroisopropene dicarboxylic anhydride (6FDA) and (ii) cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA). In one or more of the groups, the above aromatic diamine contains 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine (TFDB).

In a preferred embodiment of the present invention, the aromatic dicarbonyl compound may be selected from the group consisting of p-terephthaloyl chloride (TPC), terephthalic acid, and isophthalic acid. One or more of the group consisting of iso-phthaloyl dichloirde and 4,4'-benzoyl chloride.

In a preferred embodiment of the present invention, one or more aromatic groups selected from the group consisting of (ii) cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA) The content of dianhydride relative to the total moles of aromatic dianhydride and aromatic carbonyl compound can be I think it is 10 to 30 mol%.

In a preferred embodiment of the present invention, the aromatic diamine may further comprise a selected from the group consisting of diaminodiphenyl ether (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), and bis(amino group). Hydroxyphenyl)hexafluoropropane (DBOH), bis(aminophenoxy)benzene (133APB, 134APB, 144APB), bis(aminophenyl)hexafluoropropane (33-6F, 44-6F), bis(aminobenzene)碸(4DDS, 3DDS), bis[(aminophenoxy)phenyl]hexafluoropropane (4BDAF), bis[(aminophenoxy)phenyl]propane (6HMDA) and bis(aminophenoxy) More than one of the groups consisting of diphenyl hydrazine (DBSDA).

In a preferred embodiment of the present invention, the aromatic dianhydride may further comprise a selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] oct-7-ene-2, 3, 5, 6-tetracarboxylic dianhydride (BTA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA) , pyromellitic dianhydride, 1,2,4,5- pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), bis(carboxyphenyl) dimethyl decane dianhydride (SiDA), oxodiphthalic dianhydride (ODPA), bis(dicarboxyphenoxy)diphenyl sulfide dianhydride (BDSDA), sulfonyldiphthalic anhydride (SO2DPA) and More than one group consisting of propylene diphenoxy) bis(phthalic anhydride) (6HDBA).

Another embodiment of the present invention provides a polyamidoximine film produced from the above polyamidoximine resin.

In another preferred embodiment of the present invention, the polyamidimide film has a transmittance of 88% or more as measured at 550 nm with respect to a film having a thickness of 8 to 12 μm, according to a thermomechanical analysis method (TMA- The coefficient of thermal expansion (CTE) measured at 50 to 300 ° C satisfies 13 ppm/° C. or less.

In another preferred embodiment of the present invention, the polyimide film has a tensile strength of 130 MPa or more with respect to a film having a thickness of 8 to 12 μm as measured according to ASTM D882.

In another preferred embodiment of the present invention, the polyamidimide film has a birefringence value of 0.1 or less, a phase difference (Ro) of 1 nm or less, and a phase difference (Rth) in the thickness direction. It satisfies 300 nm or less at 10 μm.

According to another embodiment of the present invention, a substrate for a flexible display comprising the above-described polyimide film.

According to the present invention, it is possible to provide a colorless and transparent, exhibits excellent thermal stability and mechanical properties, and has improved birefringence characteristics and can be applied to a semiconductor insulating film, a TFL-LCD insulating film, a passivation film, a liquid crystal back film, and an optical communication. Polymers, solar cell protective films, flexible display substrates, and other fields of polyamidoximine resins and films thereof.

All technical and scientific terms used in the present specification have the same meaning as commonly understood by those skilled in the art, unless otherwise defined. The nomenclature used in this specification is generally a commonly used naming method well known in the art.

In the entire specification of the present invention, when a certain component is "included" with a certain component, the description is not specifically indicated, and the other components are not excluded, and the other components may be further included.

In the above and the following description, "an imidization" is defined to include a part of "amylamine", and "deuterated imide" includes a part of "amylamine".

One aspect of the present invention relates to a polyamidoximine resin obtained by copolymerizing an aromatic dianhydride and an aromatic dicarbonyl compound with an aromatic diamine. And the obtained ruthenium imide of polyamic acid. Wherein, as the aromatic dianhydride, comprising (i) 4,4'-hexafluoroisopropene dicarboxylic anhydride (6FDA) and (ii) cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic acid More than one group consisting of anhydrides (CPDA), and aromatic diamines may contain 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine ( TFDB).

Another aspect of the present invention relates to a polyamidoquinone imide film obtained from the above polyamidoximine resin, and a flexible film comprising the above polyamidoximine film Substrate for a display.

Hereinafter, the present invention will be described in more detail.

The present invention provides a polyamide and a film thereof, and a film thereof, which is excellent in thermal stability, mechanical properties, and birefringence characteristics, and can be applied to a substrate for a flexible display or the like, and a film thereof. The quinone imine resin is a ruthenium imide of polylysine obtained by copolymerization of an aromatic dianhydride, an aromatic dicarbonyl compound, and an aromatic diamine. At this time, as the aromatic dianhydride, it is selected from (i) 4,4'-hexafluoroisopropene dicarboxylic anhydride (6FDA) and (ii) cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic acid. More than one group consisting of dianhydride (CPDA). The aromatic diamine contains 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine (TFDB).

Further, the aromatic dicarbonyl compound may be selected from the group consisting of p-terephthaloyl chloride (TPC), terephthalic acid, iso-phthaloyl dichloirde, and 4,4. More than one of the group consisting of '4,4'-benzoyl chloride.

Since the aromatic dicarbonyl compound has a benzene ring, high thermal stability and mechanical properties can be achieved, but it has a high birefringence value due to this property. Further, alicyclic dianhydrides such as cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA) have low birefringence values, but lower thermal stability and mechanical properties.

However, when 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine (TFDB) is used as the diamine, thermal stability and optical properties can be improved. When the content of the aromatic dianhydride, the aromatic dicarbonyl compound, and the aromatic diamine is controlled within a specific range and polymerization is carried out as described below, thermal stability, mechanical properties, and optical properties can be simultaneously improved.

In terms of thermal stability and birefringence, the aromatic diamine which can be used in the present invention may contain, in addition to bistrifluoromethylbenzidine (TFDB), another aromatic diamine, which may be selected from two. Aminodiphenyl ether (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), bis(aminohydroxyphenyl)hexafluoropropane (DBOH), bis(aminophenoxy)benzene (133APB, 134APB) , 144APB), bis(aminophenyl)hexafluoropropane (33-6F, 44-6F), bis(aminophenyl)anthracene (4DDS, 3DDS), bis[(aminophenoxy)phenyl]hexafluoropropane (4BDAF), one of a group consisting of bis[(aminophenoxy)phenyl]propane (6HMDA) and bis(aminophenoxy)diphenyl sulfonium (DBSDA) The above, but not limited to this.

Further, the aromatic dianhydride of the present invention may comprise, in addition to thermal stability, mechanical properties and optical properties, a component selected from the group consisting of 4,4'-hexafluoroisopropene dicarboxylic anhydride (6FDA) and cyclobutane tetracarboxylic acid In addition to one or more of anhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA), other aromatic dianhydrides may be included, for example, selected from biphenyltetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene -1,2-dicarboxylic acid dianhydride (TDA), pyromellitic dianhydride, 1,2,4,5- pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), Bis(carboxyphenyl)dimethyl phthalane dianhydride (SiDA), oxydiphthalic dianhydride (ODPA), bis(dicarboxyphenoxy)diphenyl sulfide dianhydride (BDSDA), sulfonyl One or more of the group consisting of diphthalic anhydride (SO2DPA) and (isopropylidenediphenoxy) bis(phthalic anhydride) (6HDBA), but is not limited thereto.

The polyamidoximine resin of the present invention is obtained by polymerizing an aromatic diamine, an aromatic dianhydride, and an aromatic dicarbonyl compound, followed by ruthenium imidization. In order to improve thermal stability, mechanical properties, and birefringence characteristics, a polyphthalic acid solution is prepared by copolymerizing an aromatic dianhydride and an aromatic dicarbonyl compound: diamine in a ratio of 1:1. At this time, the polymerization reaction conditions are not particularly limited, and it is preferred to carry out the reaction in an inert gas atmosphere at -10 to 80 ° C for 2 to 48 hours.

In this case, in the present invention, a solvent may be used in order to carry out a solution polymerization reaction of each monomer, and the solvent is not particularly limited as long as it is a solvent capable of dissolving polyglycolic acid, and preferably selected from the group consisting of m-cresol, N-methyl-2 quinolone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl hydrazine (DMSO), acetone, diacetic acid, etc. More than one polar solvent in the group. Further, a low-boiling solution such as tetrahydrofuran (THF) or chloroform or a low-absorbent solvent such as γ-butyrolactone may be used.

The content of the above solvent is not particularly limited, but in order to obtain a molecular weight and viscosity of a suitable polyamic acid solution, the solvent content is preferably from 50 to 95% by weight, more preferably from 70 to 90% by weight based on the total amount of the polyamic acid solution. 90% by weight.

Further, the thermal stability, mechanical properties, and birefringence characteristics of the resin and the film are affected depending on the amount of the aromatic dicarbonyl compound added during the reaction. In order not to lower the inherent physical properties of the polyamidoximine, the content of the aromatic dicarbonyl compound is relative to the aromatic dianhydride and The total amount of the aromatic dicarbonyl compound is from 1 to 50 mol%, preferably from 5 to 50 mol%.

When the amount of the aromatic dicarbonyl compound relative to the total amount of the aromatic dianhydride and the aromatic dicarbonyl compound exceeds 50 mol%, the thermal stability and mechanical properties can be improved, but the yellow index or the transmittance is lowered. The optical characteristics are degraded, and in particular, the birefringence value becomes high and it is difficult to use for the display level substrate.

In addition, when the amount of the aromatic dicarbonyl compound relative to the total amount of the aromatic dianhydride and the aromatic dicarbonyl compound is less than 1 mol%, the optical properties can be improved, but the thermal stability and mechanical properties are lowered. Therefore, misalignment and tearing may occur during the preparation of the display.

Further, one or more aromatic dianhydrides selected from the group consisting of (ii) cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA), relative to aromatic dianhydrides and aromatic dicarbonyl compounds The total molar ratio, when it is 10 to 30 mol%, can uniformly improve the optical characteristics in the set wavelength range, and can uniformly improve the thermal stability and mechanical properties, and thus is a preferable reaction ratio.

When the polyamido acid solution is subjected to hydrazine imidization to prepare a polyamidoximine resin in the above manner, the ruthenium imidization method which can be used can be selected in a suitable manner in a known oxime imidization method. The method may include a method such as a thermal hydrazine imidation method, a chemical hydrazide method, a thermal hydrazide method, and a chemical hydrazide method.

The polyimide film can be obtained in the following manner. After the polymerized polyamine is formed on a support, it is prepared by the above-described hydrazylation method.

In the above chemical hydrazylation method, a dehydrating agent typified by an acid anhydride such as acetic anhydride and a quinone imine represented by a tertiary amine such as isoquinoline, β-methylpyridine or pyridine are added to the polyamic acid solution. The method for chemically catalyzing, in addition, the thermal hydrazine imidation method or the thermal hydrazylation method and the chemical hydrazine imidation method may be used in combination with the hydrazide imidation method according to the type of the polyamidic acid solution and the obtained polyfluorene. The thickness or the like of the amine quinone film is adjusted or changed.

The following is a more detailed description of an example of the preparation of a polyimide film by a composite ruthenium imidization method using the above-described thermal hydrazylation method and chemical hydrazylation method. Its After the polyamine solvent solution is added to the support by adding a dehydrating agent and a hydrazine imidization catalyst, heating is further carried out at 80 to 200 ° C, preferably 100 to 180 ° C, to obtain a dehydrating agent and a ruthenium amide catalyst. After activation, partial curing and drying, heating at 200 to 400 ° C for 5 to 400 seconds, a polyamidoximine film can be obtained.

Further, in the present invention, a polyamidoximine film can be obtained from the polyamic acid solution obtained above by the following method. That is, after the obtained polyamic acid solution is imidized, the ruthenium solution is added to the second solvent and precipitated, filtered, and dried to obtain a solid of the polyamidimide resin. The component is then obtained by dissolving the obtained solid component of the polyamidoximine resin in a first solvent, and obtaining the polyamidoximine solution through a film forming procedure.

When the above polyamic acid solution is subjected to hydrazine imidation, the above-mentioned hydrazine imidization method, chemical hydrazylation method or thermal hydrazylation method and chemical hydrazylation method may be used together. Imidization method. Specific examples of the ruthenium imidation method used in combination with the above-described hydrazine imidization method and the chemical hydrazine imidation method are as follows. A dehydrating agent and a ruthenium iodide catalyst may be added to the obtained polyamic acid solution, followed by heating at 20 to 180 ° C for 1 to 12 hours to carry out oxime imidization.

The first solvent may be the same solvent as that used in the polymerization of the polyaminic acid solution, and in order to obtain the solid component of the polyamidoximine resin, a solvent having a lower polarity than the first solvent may be used as the second solvent, which may specifically It is one or more selected from the group consisting of water, alcohols, ethers, and ketones. The content of the aforementioned second solvent is not particularly limited, and is preferably from 5 to 20% by weight based on the weight of the polyaminic acid solution.

In view of the boiling point of the second solvent, the solid content of the polyamidoximine resin obtained as described above is filtered and dried under the following conditions, preferably, the temperature is from 50 to 120 ° C for 3 to 24 hours.

Then, in the film forming process, a polyamido ruthenium imine solution in which the solid component of the polyamidoximine resin is dissolved is formed on the support, and is slowly heated in a temperature range of 40 to 400 ° C, and heated 1 A polyamidoximine film can be obtained in 8 minutes.

In the embodiment of the present invention, heat treatment is further performed on the polyimide film obtained above to remove thermal history and residual stress remaining in the film, and thus a film having stable thermal characteristics can be obtained. At this time, the temperature of the additional heat treatment is preferably 300 to 500 ° C, heat treatment The time is preferably from 1 minute to 3 hours, and the residual volatile component of the film after completion of the heat treatment is 5% or less, preferably 3% or less.

The polyamidoximine resin obtained according to the present invention satisfies the following characteristics, and has a weight average molecular weight of 150,000 to 180,000, a viscosity of 700 to 900 poise, and a glass transition temperature of 300 ° C or more.

Further, the polyamidoximine film according to the present invention has a transmittance of 88% or more and a yellowness index of 5 or less at 550 nm with respect to a film having a thickness of 8 to 12 μm, according to a thermomechanical analysis method (TMA). - Method) The coefficient of thermal expansion (CTE) measured at 50 to 300 ° C satisfies 13 ppm / ° C or less.

Further, the polyamidoximine film according to the present invention can satisfy the following conditions. When measured according to ASTM D882, the film has a tensile strength of 130 MPa or more, a birefringence value of 0.1 or less, a phase difference (Ro) of 1 nm or less, and a phase difference (Rth) in the thickness direction with respect to a film having a thickness of 8 to 12 μm. It satisfies 300 nm or less at 10 μm.

As described above, the polyimide film of the present invention is colorless and transparent, exhibits excellent thermal stability and mechanical properties, and has improved birefringence properties, and can be applied to a semiconductor insulating film, a TFL-LCD insulating film, and passivation. Various fields such as a film, a liquid crystal back film, a material for optical communication, a protective film for a solar cell, and a flexible display substrate.

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the invention is not limited to the following examples.

[Example 1]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 716 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. Further, 23.99 g (0.054 mol) of 6FDA and 7.06 g (0.036 mol) of CBDA were added, and they were dissolved and reacted for a certain period of time. Then, the temperature of the solution was maintained at 15 ° C, and then 18.27 g (0.09 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polylysine having a solid concentration of 13% by weight and a viscosity of 860 poise. Solution.

34.14 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, then cooled to room temperature, and precipitated with 20 L of methanol to precipitate the solid component. After pulverizing by filtration, it was vacuum-dried at 100 ° C for 6 hours to obtain 95 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 174,000. In the above description and the following description, the average particle diameter of the polyamidimide solid content powder is an average value measured three times using a particle size analyzer (S3500, Microtrac). In the measurement, the photopolymerized powder obtained by drying the precipitated solid component was analyzed as a sample. The weight average molecular weight analysis was carried out by dissolving the photopolymerized powder obtained by drying the precipitated solid component at a concentration of 1% in N,N-dimethylacetamide (DMAc), and then using 0.45. The μm PTFE syringe filter was filtered, and then injected into a gel permeation chromatograph, and analyzed by gel permeation chromatography (GPC) to determine the weight average molecular weight.

The above 95 g of the copolymerized polyamidoximine solid component powder was dissolved in 768 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 10 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Embodiment 2]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 744 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After further adding 31.99 g (0.072 mol) of 6FDA and 7.06 g (0.036 mol) of CBDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, after which 14.62 g (0.072 mol) of TPC was added, which was reversed at 25 ° C. It took 12 hours to obtain a polyamic acid solution having a solid content of 13% by weight and a viscosity of 830 poise.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum dried at 100 ° C for 6 hours to obtain 104 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 163,000. The above 104 g of the copolymerized polyamidoximine solid component powder was dissolved in 841 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 10 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Example 3]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 803 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After further adding 47.98 g (0.108 mol) of 6FDA and 7.06 g (0.036 mol) of CBDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 7.31 g (0.036 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polyglycine having a solid content of 13% by weight and a viscosity of 815 poise. Solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum-dried at 100 ° C for 6 hours to obtain 110 g of a solid component powder of a copolymerized amidoxime.

Particle size analysis and molecular weight fraction of polyamide nitrile solid component powder The results are as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 157,000. The above 110 g of the copolymerized polyamidoximine solid component powder was dissolved in 890 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 11 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Example 4]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 846 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After further adding 59.97 g (0.135 mol) of 6FDA and 7.06 g (0.036 mol) of CBDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 1.83 g (0.009 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polyglycine having a solid content of 13% by weight and a viscosity of 840 poise. Solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum dried at 100 ° C for 6 hours to obtain 114 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 172,000. The above 114 g of the copolymerized polyamidoximine solid component powder was dissolved in 922 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 11 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Example 5]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and while nitrogen was passed through the above reactor, 719 g of N,N-dimethylacetamide ( DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After adding 23.99 g (0.054 mol) of 6FDA and 7.57 g (0.036 mol) of CPDA, the mixture was stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 18.27 g (0.09 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours to obtain a polyamine having a solid concentration of 13% by weight and a viscosity of 790 poise. Acid solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum-dried at 100 ° C for 6 hours to obtain 90 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 151,000. The above 90 g of the copolymerized polyamidoximine solid component powder was dissolved in 728 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution thus obtained was coated on a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 11 μm polyamidoximine film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

The polyamido ruthenium imide film thus obtained was measured for linear thermal expansion coefficient at 50 to 300 ° C according to a thermomechanical analysis method. The linear thermal expansion coefficient was measured at 10.2 ppm/°C.

[Embodiment 6]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 764 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. Add another 31.99g (0.072mol) 6FDA After 7.75 g (0.036 mol) of CPDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 14.62 g (0.072 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours to obtain a polyamine having a solid concentration of 13% by weight and a viscosity of 780 poise. Acid solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, the mixture was vacuum dried at 100 ° C for 6 hours to obtain 102 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 150,000. The above 102 g of the copolymerized polyamidoximine solid component powder was dissolved in 825 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 12 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Embodiment 7]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and while nitrogen was passed through the above reactor, 806 g of N,N-dimethylacetamide was charged ( DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After further adding 47.98 g (0.108 mol) of 6FDA and 7.57 g (0.036 mol) of CPDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 7.31 g (0.036 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polyglycine having a solid content of 13% by weight and a viscosity of 790 poise. Solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum dried at 100 ° C for 6 hours. Thus, 109 g of a solid component powder of a copolymerized amidoxime is obtained.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 151,000. The above 109 g of the copolymerized polyamidoximine solid component powder was dissolved in 882 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 10 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Embodiment 8]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 849 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After 59.97 g (0.135 mol) of 6FDA and 7.57 g (0.036 mol) of CPDA were added thereto, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 1.83 g (0.009 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polyglycine having a solid content of 13% by weight and a viscosity of 815 poise. Solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum dried at 100 ° C for 6 hours to obtain 112 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 165,000. The above 112 g of the copolymerized polyamidoximine solid component powder was dissolved in 906 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 11 μm polyamidoximine film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Comparative Example 1]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 701 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After further adding 19.99 g (0.045 mol) of 6FDA and 7.06 g (0.036 mol) of CBDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 20.10 g (0.099 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polyglycine having a solid content of 13% by weight and an annual density of 870 poise. Solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum-dried at 100 ° C for 6 hours to obtain 93 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 178,000. The above 93 g of the copolymerized polyamidoximine solid component powder was dissolved in 752 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution thus obtained was coated on a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 11 μm polyamidoximine film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Comparative Example 2]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 725 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. Add 19.99g (0.045mol) 6FDA After 10.59 g (0.036 mol) of BPDA, they were stirred for a certain period of time to dissolve and react. Then, the temperature of the solution was maintained at 15 ° C, and then 20.10 g (0.099 mol) of TPC was added, and the reaction was carried out at 25 ° C for 12 hours, thereby obtaining a polyglycine having a solid content of 13% by weight and a viscosity of 855 poise. Solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum dried at 100 ° C for 6 hours to obtain 94 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 170,000. The above 94 g of the copolymerized polyamidoximine solid component powder was dissolved in 760 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 10 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Comparative Example 3]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature adjuster, and a cooler was used as a reactor, and while nitrogen was passed through the above reactor, 861 g of N,N-dimethylacetamide was charged ( DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After adding 63.97 g (0.144 mol) of 6FDA and 7.06 g (0.036 mol) of CBDA, the mixture was stirred for a certain period of time and dissolved, and reacted at 25 ° C for 12 hours to obtain a solid component concentration of 13% by weight, and the viscosity was 800poise polylysine solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum-dried at 100 ° C for 6 hours to obtain 118 g of a solid component powder of a copolymerized amidoxime.

Particle size analysis and molecular weight fraction of polyamide nitrile solid component powder The results are as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 162,000. The above 118 g of the copolymerized polyamidoximine solid component powder was dissolved in 954 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and then dried at 300 ° C for 30 minutes, then slowly cooled and separated from the plate to obtain 10 μm. Polyimide quinone film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Comparative Example 4]

A 1 L reactor equipped with a stirrer, a nitrogen injection device, a funnel, a temperature regulator, and a cooler was used as a reactor, and 840 g of N,N-dimethylacetamide was charged while passing nitrogen through the above reactor. DMAc), after adjusting the temperature of the reactor to 25 ° C, 57.64 g (0.18 mol) of TFDB was added to dissolve it, and the solution was maintained at 25 °C. After adding 63.97 g (0.144 mol) of 6FDA and 7.57 g (0.036 mol) of CPDA, the mixture was stirred for a certain period of time and dissolved, and reacted at 25 ° C for 12 hours to obtain a solid component concentration of 13% by weight, and the viscosity was 720poise of polyaminic acid solution.

34.17 g of pyridine and 44.12 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 70 ° C for 1 hour, and then cooled to room temperature, and precipitated with 20 L of methanol to precipitate a solid component. After pulverizing by filtration, it was vacuum dried at 100 ° C for 6 hours to obtain 116 g of a solid component powder of a copolymerized amidoxime.

The particle size analysis and molecular weight analysis of the polyamide amide imine solid powder were carried out, and the results were as follows. The average particle diameter was 70 to 80 μm, and the weight average molecular weight was 150,000. The above 116 g of the copolymerized polyamidoximine solid component powder was dissolved in 938 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then the solution was applied to a stainless steel plate. Then, it was molded at 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, dried at 300 ° C for 30 minutes, then slowly cooled, and separated from the plate to obtain a cluster of 11 μm. Amidoxime film. Then, the final heat treatment was performed, and heat treatment was again performed at 300 ° C for 10 minutes.

[Physical evaluation method]

(1) penetration rate

The films obtained in the examples and the comparative examples were measured for transmittance at 550 nm using a UV spectrometer (KONICA MINOLTA CM-3700d).

(2) Yellow Index (Yellow Index, Y.I.)

The yellow index was measured using a UV spectrometer (KONICA MINOLTA CM-3700d) at 550 nm in accordance with ASTM E313 specifications.

(3) Coefficient of Thermal Expansion (CTE)

The coefficient of thermal expansion was measured at 50 to 300 ° C according to TMA-Method using a thermomechanical analyzer (Perkin Elmer, Diamond TMA) at a temperature increase rate of 10 ° C/min, and a load of 100 mN was applied.

(4) Thickness measurement

Any five points of the polyimide film were selected and the thickness was measured using an Anritsu Electronic Micrometer, and the deviation of the device was ±0.5% or less.

(5) Birefringence value

The average value was calculated by measuring three times at 630 nm using a birefringence analyzer (Prism Coupler, Sairon SPA4000).

(6) Tensile Strength

The measurement was performed based on ASTM-D882 using Instron Model 5967. The size of the test piece was 13 mm x 100 mm, and the test piece was measured 7 times at a tensile rate of 50 mm/min. The maximum value and the minimum value were removed, and the average value was calculated.

(7) Delay (Retardation)

The delay was determined by using the RETS of OTSUKA ELECTRONICS. The test piece is a regular square test piece having a length and a width of 1 inch, and the test piece is attached to the sample holder, and is measured at 550 nm by a spectroscope, and Ro (phase difference in the plane direction) is measured at an incident angle of 0. To measure the in-plane birefringence, Rth (phase difference in the thickness direction) is at the incident angle The difference in thickness was measured at a position of 45 degrees.

Ro=(nx-ny)*d

Rth=[(ny-nz)*d+(nx-nz)*d]/2

Wherein nx is a refractive index in the x direction, ny is a refractive index in the y direction, nz is a refractive index in the z direction, and d is a value calculated when the thickness of the polyimide film is 10 μm.

As shown in Table 1, it is understood that the polyimide film of Examples 1 to 8 is colorless and transparent and has a low birefringence value as compared with the polyamides of Comparative Examples 1 to 4. Excellent mechanical properties and thermal stability.

A person skilled in the art can make a simple modification or modification of the invention, and such modifications or variations are considered to be included in the scope of the invention.

Claims (13)

A polyamidoquinone imine resin which is a bismuth hydride of a polyphthalic acid obtained by copolymerization of a dianhydride and an aromatic dicarbonyl compound and an aromatic diamine. The dianhydride comprises (i) 4,4'-hexafluoroisopropene dicarboxylic anhydride (6FDA) and (ii) selected from the group consisting of cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA). In one or more, the aromatic diamine comprises 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine (TFDB). The polyamidoximine resin according to claim 1, wherein the aromatic dicarbonyl compound contains 1 to 50 mol% based on the total number of moles of the dianhydride and the aromatic dicarbonyl compound. . The polyamidoximine resin according to claim 1, wherein (ii) one or more selected from the group consisting of cyclobutane tetracarboxylic dianhydride (CBDA) and cyclopentane tetracarboxylic dianhydride (CPDA) The total number of moles relative to the dianhydride and the aromatic dicarbonyl compound is from 10 to 30 mol%. The polyamidoximine resin according to claim 1, wherein the aromatic dicarbonyl compound comprises p-terephthaloyl chloride (TPC), terephthalic acid (terephthalic) One or more of the group consisting of acid), iso-phthaloyl dichloirde and 4,4'-biphenyldicarbonyl chloride. The polyamidoximine resin according to claim 1, wherein the aromatic diamine further comprises a selected from the group consisting of diaminodiphenyl ether (ODA), p-phenylenediamine (pPDA), and m-phenylenediamine. (mPDA), bis(aminohydroxyphenyl)hexafluoropropane (DBOH), bis(aminophenoxy)benzene (133APB, 134APB, 144APB), bis(aminophenyl)hexafluoropropane (33-6F, 44-) 6F), bis(aminophenyl)phosphonium (4DDS, 3DDS), bis[(aminophenoxy)phenyl]hexafluoropropane (4BDAF), bis[(aminophenoxy)phenyl]propane (6HMDA) and One or more of the groups consisting of bis(aminophenoxy)diphenylphosphonium (DBSDA). The polyamidoximine resin according to claim 1, wherein the dianhydride further comprises a selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA) and bicyclo [2.2.2] oct-7-ene-2. ,3,5,6-tetracarboxylic dianhydride (BTA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Diacetic anhydride (TDA), pyromellitic dianhydride, 1,2,4,5- pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), bis(carboxyphenyl) dimethyl Decane dianhydride (SiDA), oxydiphthalic dianhydride (ODPA), bis(dicarboxyphenoxy)diphenyl sulfide dianhydride (BDSDA), sulfonyl diphthalic anhydride (SO2DPA) And one or more of the group consisting of (isopropylidenediphenoxy) bis(phthalic anhydride) (6HDBA). A polyamidoximine film produced by the polyamidoximine resin according to any one of claims 1 to 6. The polyamidoximine film according to claim 7, wherein the polyimide film has a transmittance of 88% or more at 550 nm with respect to a film having a thickness of 8 to 12 μm. The coefficient of thermal expansion (CTE) measured at 50 to 300 ° C according to the thermomechanical analysis method (TMA-Method) was 13 ppm/° C. or less. The polyamidimide film according to claim 7, wherein the polyimide film has a tensile strength of 130 MPa or more with respect to a film having a thickness of 8 to 12 μm as measured according to ASTM D882. The polyamidoximine film according to claim 7, wherein the polyimide film has a birefringence value of 0.1 or less, a phase difference (Ro) of 1 nm or less, and a thickness direction. The phase difference (Rth) on the upper side is 300 nm or less at 10 μm. A polyamidoximine film comprising the polyamidoximine resin according to any one of claims 1 to 6. A substrate for a flexible display comprising the polyamidimide film according to any one of claims 1 to 6. A substrate for a flexible display comprising the polyamidimide film as described in claim 11 of the patent application.